JP2013166725A - Phenols and process for production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide novel phenols becoming a fundamental structure of a ligand applicable to a catalytic reaction and a process for production thereof.SOLUTION: Phenols are shown by general formula (1). (In the formula, Rto Rrepresent samely or differently an alkyl group, a phenyl group, or a polycyclic aromatic hydrocarbon group, at least one of Rto Rrepresents a polycyclic aromatic hydrocarbon group, Rto Rrepresent samely or differently a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, a fluorinated hydrocarbon group, an alkoxy group, an aryloxy group, a secondary amino group or a tertiary silyl group, and Rto Rmay arbitrarily bind).

Description

  The present invention relates to phenols and a method for producing the same.

  Phenol having an aralkyl group at the ortho position can be used for various derivatives, and its use for a basic skeleton of a ligand has been reported (Non-patent Document 1). The metal complex using this ligand can be used for various catalytic reactions, and a polymerization catalyst is one of the application examples (Patent Document 1, Non-Patent Document 2). Due to its usefulness, various methods for synthesizing phenols having an aralkyl group at the ortho position have been reported, and Friedel-Crafts reaction is known as the main synthesis method (Non-patent Documents 3 and 4).

  However, it is known that a compound having a polycyclic aromatic hydrocarbon group has higher electrophilic substitution reactivity than a compound having a phenyl group. When synthesizing phenols with aralkyl groups containing polycyclic aromatic hydrocarbon groups by Friedel-Crafts reaction, the electrophilic substitution reaction to undesired polycyclic aromatic hydrocarbon groups is suppressed due to the difference in reactivity. There was a need. Therefore, almost no synthesis examples of phenols having a polycyclic aromatic hydrocarbon skeleton as an aralkyl group have been reported.

JP 2008-239608A

Journal of Organic Chemistry, 2009, Volume 74, P. 753. Macromolecules, 2004, Volume 37, P. 8201. Journal of Organic Chemistry, 1999, Volume 64, P. 8812. Chemistry. A European Journal, 2009, Volume 15, P. 793.

  The problem to be solved by the present invention is to provide new phenols that serve as a basic skeleton of a ligand that can be used for catalysis and a method for producing the same.

  The present inventor has found that the above-described problems can be solved by the present invention through intensive studies.

（式中、Ｒ^１〜Ｒ^３は同一または相異なり、アルキル基、フェニル基、または多環芳香族炭化水素基を示し、Ｒ^１〜Ｒ^３のいずれか少なくとも１つは多環芳香族炭化水素基であり、Ｒ^４〜Ｒ^７は同一または相異なり、水素原子、ハロゲン原子、アルキル基、アラルキル基、フッ素化炭化水素基、アルコキシ基、アリールオキシ基、第二級アミノ基または第三級シリル基を示し、Ｒ^４〜Ｒ^７は任意に結合していてもよく、Ｒ¹〜Ｒ^７における、フェニル基、アリールオキシ基、多環芳香族炭化水素基は置換基を有していてもよい。） The present invention relates to a phenol represented by the general formula (1).

(Wherein R ^{1 to} R ³ are the same or different and represent an alkyl group, a phenyl group, or a polycyclic aromatic hydrocarbon group, and at least one of R ^{1 to} R ³ is a polycyclic aromatic hydrocarbon) R ^{4 to} R ⁷ are the same or different and are a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, a fluorinated hydrocarbon group, an alkoxy group, an aryloxy group, a secondary amino group or a tertiary silyl group. R ^{4 to} R ⁷ may be optionally bonded, and the phenyl group, aryloxy group, and polycyclic aromatic hydrocarbon group in R ^{1 to} R ⁷ may have a substituent. .)

（式中、Ｒ^４〜Ｒ^７は同一または相異なり、水素原子、ハロゲン原子、アルキル基、フェニル基、フェニル基、アラルキル基、フッ素化炭化水素基、アルコキシ基、アリールオキシ基、第二級アミノ基または第三級シリル基を示し、Ｒ^４〜Ｒ^７は任意に結合していてもよく、Ｒ⁴〜Ｒ^７における、フェニル基、アリールオキシ基は置換基を有していてもよい。）

（式中、Ｒ^１〜Ｒ^３は同一または相異なり、アルキル基、フェニル基、または多環芳香族炭化水素基を示し、Ｒ^１〜Ｒ^３のいずれか少なくとも１つは多環芳香族炭化水素基であり、Ａ^１はハロゲン原子または水酸基を表し、Ｒ^１〜Ｒ^３における、フェニル基、多環芳香族炭化水素基は置換基を有していてもよい。）

（式中、Ｒ^１、Ｒ^２は同一または相異なり、アルキル基、フェニル基、または多環芳香族炭化水素基を示し、Ｒ^１またはＲ^２の少なくとも１つは多環芳香族炭化水素基であり、Ｒ^８は水素原子またはアルキル基を表し、Ｒ^１〜Ｒ^２における、フェニル基、多環芳香族炭化水素基は置換基を有していてもよい。）
The present invention also relates to a production method comprising reacting a mixture of an acidic compound and a compound represented by the general formula (2) with a compound represented by the general formula (3) or the general formula (4). .

(Wherein R ^{4 to} R ⁷ are the same or different and are a hydrogen atom, halogen atom, alkyl group, phenyl group, phenyl group, aralkyl group, fluorinated hydrocarbon group, alkoxy group, aryloxy group, secondary amino group) A group or a tertiary silyl group, R ^{4 to} R ⁷ may be optionally bonded, and the phenyl group and aryloxy group in R ^{4 to} R ⁷ may have a substituent.)

(Wherein R ^{1 to} R ³ are the same or different and represent an alkyl group, a phenyl group, or a polycyclic aromatic hydrocarbon group, and at least one of R ^{1 to} R ³ is a polycyclic aromatic hydrocarbon) A ¹ represents a halogen atom or a hydroxyl group, and the phenyl group and polycyclic aromatic hydrocarbon group in R ^{1 to} R ³ may have a substituent.)

(Wherein R ¹ and R ² are the same or different and represent an alkyl group, a phenyl group, or a polycyclic aromatic hydrocarbon group, and at least one of R ¹ or R ² is a polycyclic aromatic hydrocarbon group; And R ⁸ represents a hydrogen atom or an alkyl group, and the phenyl group and polycyclic aromatic hydrocarbon group in R ^{1 to} R ² may have a substituent.

  ADVANTAGE OF THE INVENTION According to this invention, the new phenol used as the basic skeleton of the ligand which can be utilized for a catalytic reaction, and its manufacturing method can be provided.

The phenol represented by the general formula (1) will be described.

R ^{1 to} R ³ are the same or different and represent an alkyl group, a phenyl group, or a polycyclic aromatic hydrocarbon group, and the phenyl group and the polycyclic aromatic hydrocarbon group in R ^{1 to} R ³ have a substituent. You may do it. At least one of R ^{1 to} R ³ is a polycyclic aromatic hydrocarbon group, preferably one of R ^{1 to} R ³ is a polycyclic aromatic hydrocarbon group, more preferably R ^1. one either to R ³ is a polycyclic aromatic hydrocarbon group is any two of the alkyl group.

Examples of the alkyl group of R ^{1 to} R ³ include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a t-amyl group, and the like, and preferably a methyl group, an ethyl group, or a propyl group. More preferably a methyl group or an ethyl group, and most preferably a methyl group.

Examples of the phenyl group of R ^{1 to} R ³ include a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, a 2,3-xylyl group, a 2,4-xylyl group, and a 2,5-xylyl group. Group, 2,6-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,3,4,5-tetramethylphenyl Group, 2, 3, 4, 6-tetramethylphenyl group, pentamethylphenyl group, etc., preferably 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2, 4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, pentamethylphenyl group.

The polycyclic aromatic hydrocarbon group R ¹ to R ^3, for example, naphthyl group, anthracenyl group, phenanthryl group, naphthacenyl group, pentacenyl group, benzopyrenyl group, chrysenyl group, pyrenyl group, triphenylenyl group, etc. coronenyl group Of these, preferred are a naphthyl group, an anthracenyl group, a naphthacenyl group, and a pyrenyl group, and more preferred are a naphthyl group and an anthracenyl group.

R ^{4 to} R ⁷ are the same or different and are a hydrogen atom, a halogen atom, an alkyl group, a phenyl group, an aralkyl group, a fluorinated hydrocarbon group, an alkoxy group, an aryloxy group, a secondary amino group, or a tertiary silyl group. R4 to R7 may be arbitrarily bonded.

R ⁴ , R ⁶ , and R ⁷ are preferably hydrogen atoms, and R ⁵ is preferably a halogen atom, an alkyl group, an alkyl group, a phenyl group, a substituted phenyl group, an aralkyl group, or a fluorinated hydrocarbon group. An alkoxy group, an aryloxy group, a secondary amino group or a tertiary silyl group, more preferably a halogen atom, an alkyl group, a phenyl group, a substituted phenyl group, an aralkyl group, a fluorinated hydrocarbon group, an alkoxy group, An aryloxy group, a secondary amino group or a tertiary silyl group, and most preferably a halogen atom, an alkyl group, a fluorinated hydrocarbon group or a tertiary silyl group.

Examples of the halogen atom of R ^{4 to} R ⁷ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferable.

Examples of the alkyl group of R ^{4 to} R ⁷ include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, an i-butyl group, a s-butyl group, a t-butyl group, and a t-amyl group. Preferably methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl group, t-butyl group, more preferably methyl group, ethyl group, i-propyl group, t-butyl group. A butyl group, most preferably a methyl group and a t-butyl group.

Examples of the phenyl group of R ^{4 to} R ⁷ include a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, a 2,3-xylyl group, a 2,4-xylyl group, and a 2,5-xylyl group. Group, 2,6-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,3,4,5-tetramethylphenyl Group, 2, 3, 4, 6-tetramethylphenyl group, pentamethylphenyl group, etc., preferably phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, and pentamethylphenyl group.

Examples of the aralkyl group of R ^{4 to} R ⁷ include 1-phenyl-1-methylethyl group, 1-methyl-1- (o-toluyl) ethyl group, 1-methyl-1- (m-toluyl) ethyl group, 1 -Methyl-1- (p-toluyl) ethyl group, 1-ethyl-1-phenylethyl group, 1-ethyl-1- (o-toluyl) ethyl group, 1-ethyl-1- (m-toluyl) ethyl group 1-ethyl-1- (p-toluyl) ethyl group, 1-ethyl-1- (p-toluyl) ethyl group, 1-ethyl-1-phenylbutyl group, 1-ethyl-1- (o-toluyl) Butyl group, 1-ethyl-1- (m-toluyl) butyl group, 1-ethyl-1- (p-toluyl) butyl group, 1-ethyl-1- (p-toluyl) butyl group, 1,1-diphenyl And ethyl group, 1,1-diphenylbutyl group, 1,1,1-triphenylmethyl group, etc., preferably 1-phenyl-1-methylethyl group, 1-ethyl-1-phenylbutyl group, 1, 1-diphenylethyl group, 1,1,1-triphenylmethyl group.

Examples of the fluorinated hydrocarbon group for R ^{4 to} R ⁷ include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 1-fluoroethyl group, a 2-fluoroethyl group, a 1,1-difluoroethyl group, 1 , 2-difluoroethyl group, 2, 2-difluoroethyl group, 1, 1, 2-trifluoroethyl group, 1, 2, 2-trifluoroethyl group, 2, 2, 2-trifluoroethyl group, 1, Fluorinated alkyl groups having 1 to 6 carbon atoms such as 1, 2, 2-tetrafluoroethyl group, 1, 2, 2, 2-tetrafluoroethyl group, pentafluoroethyl group, pentafluorophenyl group, and fluorinated phenyl Groups, preferably a perfluoroalkyl group or a perfluorophenyl group.

Examples of the alkoxy group of R ^{4 to} R ⁷ include a methoxy group, an ethoxy group, a propoxy group, an i-propoxy group, a butoxy group, an i-butoxy group, and an s-butoxy group.

Examples of the aryloxy group for R ^{4 to} R ⁷ include a phenoxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, and a 4-methylphenoxy group.

Examples of the secondary amino group of R ^{4 to} R ⁷ include a dimethylamino group, a diethylamino group, a propylamino group, a dipropylamino group, a di-i-propylamino group, a di-i-butylamino group, a di- Examples thereof include s-butylamino group, di-t-butylamino group, diphenylamino group and the like.

As the tertiary silyl group of R ^{4 to} R ⁷ , for example, trimethylsilyl group, triethylsilyl group propylsilyl group, tripropylsilyl group, tri-i-propylsilyl group, tri-i-butylsilyl group, tri-s- Examples include butylsilyl group, tri-t-butylsilyl group, triphenylsilyl group, etc.

Specific examples of the phenol represented by the general formula (1) include the following compounds.

In addition, for example, a group corresponding to R ⁵ of these compounds may be a hydrogen atom, an ethyl group, an isopropyl group, a t-butyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a trifluoromethyl group, or trimethylsilyl. A compound substituted with a group can also be mentioned.

Preferable examples of the phenol represented by the general formula (1) include the following compounds.

In addition, for example, compounds in which a group corresponding to R ⁵ of these compounds is substituted with a t-butyl group can also be mentioned.

More preferable examples of the phenol represented by the general formula (1) include the following compounds.

In addition, for example, compounds in which a group corresponding to R ⁵ of these compounds is substituted with a t-butyl group can also be mentioned.

  The phenol represented by the general formula (2) will be described.

R ^{4 to} R ⁷ in the general formula (2) are the same as the above-described groups in R ^{4 to} R ⁷ in the general formula (1).

Specific examples of the phenol represented by the general formula (2) include the following compounds.

  The compound represented by the general formula (3) will be described.

R ^{1 to} R ³ in the general formula (3) are the same as the groups in R ^{1 to} R ³ in the general formula (1), and A ¹ represents a halogen atom or a hydroxyl group.

Examples of the halogen atom for A ¹ include a chlorine atom, a bromine atom, and an iodine atom.

Specific examples of the compound represented by the general formula (3) include the following compounds.

In addition, for example, compounds in which a group corresponding to A ¹ of these compounds is substituted with a bromine atom, an iodine atom, or a hydroxyl group can be exemplified.

  The compound represented by the general formula (4) will be described.

R ¹ or R ² in the general formula (4) is the same as the aforementioned group in R ¹ or R ² in the general formula (1), and R ⁸ represents a hydrogen atom or an alkyl group.

Examples of the alkyl group for R ⁸ include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, and a t-amyl group, preferably a methyl group, an ethyl group, and a propyl group, and more preferably A methyl group and an ethyl group are preferable, and a methyl group is most preferable.

  Specific examples of the compound represented by the general formula (4) include the following compounds.

  Examples of the acidic compound in the present invention include inorganic Bronsted acids such as sulfuric acid, hydrochloric acid and phosphoric acid; organic sulfonic acids such as p-toluenesulfonic acid and methanesulfonic acid; formic acid, acetic acid, trifluoroacetic acid and oxalic acid. Carboxylic acids: trimethylsilyl halide, boron trifluoride complex, titanium tetraalkoxide, aluminum chloride, iron (III) chloride, zinc chloride, titanium tetrachloride, dialkyltin oxide, dialkyltin dicarboxylate, monoalkyltin tricarboxylate Lewis acids such as tin dicarboxylate, tin tetrachloride, zirconium tetraalkoxide, zirconium tetrachloride, lead compound, bismuth compound, antimony compound, metal triflate, metal tetrafluoroborate salt, metal acetylacetonate salt; clay, active Clay, acid clay, silica, alumina, zeolites, and solid acid catalysts such as such as cation exchange resins.

  In the present invention, the amount of the compound represented by the general formula (3) or the general formula (4) is such that the molar ratio with respect to the compound represented by the formula (2) is 0.001 to 10, preferably 0. 0.01 to 10, more preferably 0.05 to 2.0, still more preferably 0.05 to 1.5, and particularly preferably 0.1 to 1.0.

  In the present invention, among the acidic compounds, the amount of inorganic Bronsted acids, organic sulfonic acids, carboxylic acids and Lewis acids used is such that the molar ratio to the compound represented by formula (3) or formula (4) is 0. 0.001 to 10, preferably 0.001 to 5, more preferably 0.001 to 2.0, still more preferably 0.005 to 1.5, and particularly preferably 0.005. 1.0.

In this reaction, the compound represented by the general formula (2), the compound represented by the general formula (3), and the compound represented by the general formula (4) may be used by dissolving in a solvent.

Examples of the solvent for dissolving the compound represented by the general formula (2) include aliphatic hydrocarbons such as hexane, heptane, octane, and cyclohexane; cyclic ethers such as 1,4-dioxane and tetrahydrofuran; dichloromethane, chloroform Halogenated hydrocarbons such as 1,2-dichloroethane and chlorobenzene, preferably hexane, heptane, octane, cyclohexane, 1,4-dioxane, dichloromethane, 1,2-dichloroethane, chlorobenzene, more preferably , Hexane, heptane, octane, cyclohexane.

  Examples of the solvent for dissolving the compound represented by the general formula (3) and the compound represented by the general formula (4) include the same solvents as those for dissolving the compound represented by the above general formula (2). I can do it.

  Although there is no restriction | limiting in particular, the usage-amount of the solvent with respect to the compound represented by General formula (2) can be used in the range used as 0 to 1000 weight times, Preferably it is 1 to 100 weight times.

The amount of the solvent used for the compound represented by the general formula (3) and the compound represented by the general formula (4) is not particularly limited, but can be used in a range of 0 to 1000 times by weight, Preferably, it is 1 to 100 times by weight.

  The form of reacting the compound represented by the general formula (3) or the general formula (4) with the mixture of the acidic compound and the compound represented by the general formula (2) is not particularly limited, but preferably Is preferably obtained by dropping a compound represented by the general formula (3) or the general formula (4) in a solvent into a mixture of the acidic compound and the compound represented by the general formula (2).

  In the present invention, the reaction temperature of the compound represented by the formula (2) is −50 ° C. to 200 ° C., preferably 0 to 200 ° C., more preferably 60 to 180 ° C., still more preferably, It is 80-180 degreeC, Most preferably, it is 80-150 degreeC.

  The production method of the present invention can be carried out in a helium, argon or nitrogen stream, or in an air atmosphere.

  In the production method of the present invention, the influence of pressure is negligible, so the reaction is generally carried out under atmospheric pressure.

  In the present invention, the reaction time of the compound represented by the general formula (2) is 5 minutes to 48 hours, preferably 5 minutes to 24 hours, more preferably 5 minutes to 3 hours.

After completion of the reaction, the reaction solution is preferably post-treated to obtain the compound represented by the general formula (1). As the post-treatment method, for example, water, dilute hydrochloric acid aqueous solution, sodium thiosulfate or sodium hydrogen carbonate-sodium carbonate mixed aqueous solution is added to the reaction solution, and then toluene, dichloromethane, hexane, ethyl acetate or diethyl ether is added to perform the extraction operation. It can be performed.
The obtained compound represented by the general formula (1) is subjected to purification by thin-phase or column chromatography using activated carbon, distillation, recrystallization, silica gel or alumina, and preparative liquid chromatography as necessary. , Can increase the purity.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The measured value of each item in an Example was measured with the following method.

The compound was identified by ¹ H NMR and gas chromatograph mass spectrometer. ¹ H NMR was measured using a nuclear magnetic resonance apparatus (manufactured by JEOL Ltd., JNM-AL400) under the following conditions. Based on the hydrogen chemical shift value of tetramethylsilane.
Measuring solvent: CDCl ₃
Measurement temperature: room temperature

The purity of the target compound was measured under the following conditions using a gas chromatograph (manufactured by Shimadzu Corporation, GC-17A) and a gas chromatograph mass spectrometer (manufactured by Shimadzu Corporation, GCMS-QP5000 / QP5050A).
(1) Measurement column: DB-1 (manufactured by Agilent Technologies)
30m long, I.V. D. (Inner diameter): 0.25 mm, Films: 0.25 μm
(2) Measurement temperature: 100 ° C. to 300 ° C. (temperature rise at 10 ° C./min) Hold at 300 ° C. for 20 minutes

The measured value of each item of the polymer obtained in the reference example was measured by the following method.
(1) Melting point Thermal analyzer A measurement was performed by the following method using a differential scanning calorimeter (manufactured by Diamond DSC Perkin Elmer).
1) Hold about 10 mg of sample under nitrogen atmosphere at 150 ° C. for 5 minutes 2) Cooling 150 ° C. to 20 ° C. (5 ° C./min) Hold for 2 minutes 3) Measurement 20 ° C. to 150 ° C. (5 ° C./min)
(2) Molecular weight and molecular weight distribution The polystyrene equivalent weight average molecular chain length (Aw) and polystyrene equivalent number average molecular chain length (An) of each polymer were calculated by gel permeation chromatography (GPC) under the following measurement conditions. . A calibration curve was prepared using standard polystyrene. 41.3 was used as the Q factor of polystyrene.
<Measurement conditions>
Apparatus: TSK HLC-8121GPC / HT (manufactured by Tosoh Corporation)
Column: TSKgel GMHHR-H (20) 2 Measurement temperature: 152 ° C
Solvent: o-dichlorobenzene (0.05% BHT added)
Solvent flow rate: 1 ml / min
Sample concentration: 0.05%
Column and sample for calibration: TSK standard polystyrene F-2000 to A-1000 (manufactured by Tosoh Corporation)
The weight average molecular weight (Mw) and number average molecular weight (Mn) of polyethylene are determined based on the polystyrene-converted weight average molecular chain length (Aw) and number average molecular chain length (An) measured under the above measurement conditions. The factor was calculated from the following formula with 17.7.
Molecular weight (Mw, Mn) = molecular chain length (Aw, An) × Q factor (3) long chain branching (LCB) number calculation method Peak top at 5 to 50 ppm in ¹³ C-NMR spectrum measured under the following measurement conditions The area of the peak derived from methine carbon to which branches having 7 or more carbon atoms are bonded when the total sum of the areas of all peaks having 1000 is 1000 is the number of long chain branches per 1000 carbons (7 or more carbon atoms) Branch number). Under the present measurement conditions, the number of long chain branches (the number of branches having 7 or more carbon atoms) was determined from the peak area having a peak top in the vicinity of 38.22 to 38.27 ppm. The peak area was in the range from the chemical shift of the valley with the peak adjacent on the high magnetic field side to the chemical shift of the valley with the peak adjacent on the low magnetic field side.
<Measurement conditions>
Apparatus: Bruker AVANCE 600 10 mm cryoprobe measurement solvent: 1,2-dichlorobenzene / 1,2-dichlorobenzene-d ₄ = 75/25 (volume ratio) mixture measurement temperature: 130 ° C.
Measurement method: Proton decoupling method Pulse width: 45 ° Pulse repetition time: 4 seconds Standard of chemical shift value: Tetramethylsilane (4) Calculation method for number of terminal vinyl groups In the ¹ H NMR spectrum of polyethylene measured under the following measurement conditions When the area in the range of 0.5 to 2.5 ppm is 1000, the peak area of 4.92 to 5.20 ppm is defined as the number of terminal vinyl groups per 1000 carbons.
^<1 H-NMR measurement conditions>
Device: EX-270 manufactured by JEOL
Measurement solvent: 1,1,2,2-tetrachloroethane-d ₂
Measurement temperature: 135 ° C
Pulse width: 30 degree pulse repetition time: 4 seconds Chemical shift value standard: The peak of 1,1,2,2-tetrachloroethane was 6.0 ppm.
(5) Intrinsic viscosity ([η]) (unit: dl / g)
Using an Ubbelohde viscometer, tetralin was used as a solvent at a measurement temperature of 135 ° C.
Example 1
Synthesis of 4-tert-butyl-2- (1-methyl-1-naphthylethyl) phenol Nitrogen-substituted 50 mL Schlenk with 6.6 g (44 mmol) of 4-tert-butylphenol and 73 mg of p-toluenesulfonic acid monohydrate (0.38 mmol) and 20 mL heptane were added and heated to 100 ° C. A solution prepared by dissolving 3.7 g (22 mmol) of isopropenylnaphthalene in 5 mL of heptane was added dropwise thereto and stirred at 100 ° C. for 1 hour. The reaction solution was analyzed by gas chromatography. The conversion of isopropenylnaphthalene to the desired product was 69%. The reaction solution was poured into an aqueous sodium bicarbonate solution. The organic layer was dried over anhydrous magnesium sulfate, and the volatile component was distilled off under reduced pressure. The obtained white solid was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 10) to give 3.0 g of 4-tert-butyl-2- (1-methyl-1-naphthylethyl) phenol. 43%) was obtained as a white solid.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
1.38 (s, 9H), 1.79 (s, 6H), 4.34 (s, 1H), 6.66 (d, J = 8 Hz, 1H), 7.19-7.30 (m, 2H), 7.44-7.54 (m, 3H) , 7.75-7.92 (m, 4H).
(Comparative Example 1)
To 100 mL Schlenk purged with nitrogen, 6.6 g (44 mmol) of 4-tert-butylphenol, 3.7 g (22 mmol) of isopropenylnaphthalene and 20 mL of dichloromethane were added. Here, 73 mg (0.38 mmol) of p-toluenesulfonic acid monohydrate was added, and the mixture was stirred at 80 ° C. for 1 hour. The reaction solution was analyzed by gas chromatography. The conversion of isopropenylnaphthalene to the desired product was 28%.
(Comparative Example 2)
4-tert-butylphenol 13.2 g (88 mmol), isopropenylnaphthalene 7.4 g (44 mmol) and cyclohexane 50 mL were added to nitrogen-substituted 50 mL Schlenk, and heated to 80 ° C. Here, 73 mg (0.38 mmol) of p-toluenesulfonic acid monohydrate was added, and the mixture was stirred at room temperature for 2 hours. The reaction solution was analyzed by gas chromatography. The conversion of isopropenylnaphthalene to the target product was 10%.
(Reference Example 1)
Synthesis of trans-1,2-bis (5-tert-butyl-2-hydroxy-3- (1-methyl-1-naphthylethyl) benzylsulfanyl) cyclooctane (1) 4-tert-butyl-2-hydroxymethyl Synthesis of -6- (1-methylcyclohexyl) phenol In a 500 mL flask purged with nitrogen, 1.7 g (5.4 mmol) of 4-tert-butyl-2- (1-methyl-1-naphthylethyl) phenol, 2.0 g of magnesium chloride ( 20 mmol), 0.9 g (30 mmol) of paraformaldehyde and 20 mL of tetrahydrofuran were added. Triethylamine 2.8 mL (20 mmol) was added here, and it heated and refluxed for 3 hours. The reaction solution was allowed to cool to room temperature, and the insoluble material was filtered off. After evaporating volatile components from the filtrate under reduced pressure, ethyl acetate and water were added to the residue. The organic layer was washed with 1 M HCl, saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 4.0 g of a mixture containing 5-tert-butyl-3- (1-methyl-1-naphthylethyl) salicylaldehyde (yield 73%).
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
1.37 (s, 9H), 1.83 (s, 6H), 4.34 (s, 1H), 7.2 to 7.9 (m, 9H), 9.82 (s, 1H), 11.2 (s, 1H).
1.4 g of the above mixture, 10 mL of tetrahydrofuran and 10 mL of methanol were added to a 200 mL flask purged with nitrogen. Sodium borohydride 160 mg (4.2 mmol) was slowly added here, and it heated up to room temperature, and stirred for 1 hour. After distilling off volatile components from the reaction solution under reduced pressure, water and ethyl acetate were added. The organic layer was washed with 1 M HCl, saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous magnesium sulfate. The resulting colorless oil was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 10 to 1: 3) to give 4-tert-butyl-2-hydroxymethyl-6- (1-methyl- 1.3 g (91% yield) of 1-naphthylethyl) phenol was obtained as a white solid.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
1.37 (s, 9H), 1.80 (s, 6H), 2.08 (t, J = 6 Hz, 1H), 4.62 (d, J = 6 Hz, 2H), 5.60 (s, 1H), 7.1 to 7.9 (m , 9H).
(2) Synthesis of 5-tert-butyl-2-hydroxy-3- (1-methyl-1-naphthylethyl) benzyl bromide In a 500 mL flask purged with nitrogen, 4-tert-butyl-2-hydroxymethyl-6- ( 1-Methyl-1-naphthylethyl) phenol 1.3 g (3.6 mmol) and dichloromethane 10 mL were added. To this was added 2.7 mL of phosphorus tribromide (1.0 M in dichloromethane, 2.7 mmol), and the mixture was stirred at room temperature for 2 hours. Water was added to the reaction solution, and the organic layer was further washed twice with water and then with saturated brine. The organic layer was dried over anhydrous magnesium sulfate, and the volatile component was distilled off under reduced pressure to give 1.5 g of 5-tert-butyl-2-hydroxy-3- (1-methyl-1-naphthylethyl) benzyl bromide (recovery). Yield> 99%) as a pale yellow oil.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
1.30 (s, 9H), 1.79 (s, 6H), 4.43 (s, 2H), 7.2 to 8.0 (m, 9H).
(3) Synthesis of trans-1,2-bis (5-tert-butyl-2-hydroxy-3- (1-methyl-1-naphthylethyl) benzylsulfanyl) cyclooctane -tert-Butyl-2-hydroxy-3- (1-methyl-1-naphthylethyl) benzyl 1.1 g (2.5 mmol), trans-cyclooctane-1,2-dithiol 0.18 g (1.0 mmol) and tetrahydrofuran 7 mL In addition, it was ice-cooled. Triethylamine 0.70 mL (5.1 mmol) was added here, and it stirred at 0 degreeC for 1 hour, and 2 hours at room temperature. Volatile components were distilled off under reduced pressure, and ethyl acetate and an aqueous ammonium chloride solution were added to the resulting residue. The organic layer was further washed with an aqueous ammonium chloride solution and saturated brine in that order, and then dried over anhydrous magnesium sulfate. After the solvent was distilled off under reduced pressure, trans-1,2-bis (5-tert-butyl-2-hydroxy-) was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 10). 0.9 g (yield> 99%) of 3- (1-methyl-1-naphthylethyl) benzylsulfanyl) cyclooctane was obtained as a pale yellow solid.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
0.8 ~ 1.8 (m, 42H), 2.46 (m, 2H), 2.51 (m, 4H), 3.51 (m, 4H), 5.72 (s, 2H), 6.99 (d, J = 2 Hz, 2H), 7.20 ~ 7.23 (m, 2H), 7.35 ~ 7.44 (m, 6H), 7.60 ~ 7.89 (m, 8H).
(Reference Example 2)
Synthesis of [cyclooctanediyl-trans-1,2-bis (5-tert-butyl-2-hydroxy-3- (1-methyl-1-naphthylethyl) benzylsulfanyl)] dichlorohafnium in a glove box under nitrogen atmosphere , Trans-1,2-bis (5-tert-butyl-2-hydroxy-3- (1-methyl-1-naphthylethyl) benzylsulfanyl) cyclooctane 170 mg (0.20 mmol) in toluene (50 mL Schlenk tube) A solution of 100 mg (0.20 mmol) of dichloro [1,1′-oxybis [ethane]] [bis (phenylmethyl) hafnium]] in toluene (1 mL) was added dropwise to the solution at room temperature. After 1.5 hours, volatile components were distilled off under reduced pressure. The obtained residue was washed with pentane and dried under reduced pressure to give [cyclooctanediyl-trans-1,2-bis (5-tert-butyl-2-hydroxy-3- (1-methyl-1-naphthyl Ethyl) benzylsulfanyl)] dichlorohafnium 110 mg (51% yield) was obtained as a white powder.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
0.50 ~ 2.2 (m, 56H), 2.48 (d, J = 14 Hz, 2H), 3.28 (d, J = 14 Hz, 2H), 6.58 (s, 2H), 6.97 (d, J = 8 Hz, 2H ), 7.3-7.5 (m, 6H), 7.59 (s, 2H), 7.68 (d, J = 6 Hz, 2H), 7.84 (d, J = 7 Hz, 2H), 8.10 (s, 2H).
(Reference Example 3)
The autoclave with a stirrer with an internal volume of 400 mL was vacuum-dried and replaced with argon, and then 200 mL of toluene was charged as a solvent, and the temperature of the reactor was raised to 40 ° C. After the temperature rise, the feed was carried out while adjusting the ethylene pressure to 0.6 MPa, and 139 mg of d-MAO was added, followed by [cyclooctanediyl-trans-1,2-bis (5-tert-butyl-2-hydroxy- 3- (1-Methyl-1-naphthylethyl) benzylsulfanyl)] dichlorohafnium (0.5 mmol / L, toluene solution) was added in an amount of 0.10 mL (0.050 μmol) to initiate polymerization. Polymerization was carried out for 60 minutes while maintaining the temperature at 40 ° C. About the obtained polymer, melting | fusing point, molecular weight and molecular weight distribution, intrinsic viscosity, the number of long chain branches, and the number of terminal vinyl groups were measured according to the measurement conditions mentioned above. Activity 4.8 × 10 ⁷ g / mol / h, melting point 117 ° C., Mw 77,000, Mn 18,800, Mw / Mn 4.1, [η] 1.4, long chain branch number 0.23 / 1000C, vinyl terminal It was 0.37 / 1000C.

Claims (2)

Phenols represented by general formula (1).

(Wherein R ^{1 to} R ³ are the same or different and represent an alkyl group, a phenyl group, or a polycyclic aromatic hydrocarbon group, and at least one of R ^{1 to} R ³ is a polycyclic aromatic hydrocarbon) R ^{4 to} R ⁷ are the same or different and are a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, a fluorinated hydrocarbon group, an alkoxy group, an aryloxy group, a secondary amino group or a tertiary silyl group. A group, R ^{4 to} R ⁷ may be optionally bonded.) It is a manufacturing method of the compound represented by General formula (1) of Claim 1, Comprising: The mixture of the compound represented by an acidic compound and General formula (2), and General formula (3) or General formula (4) And a compound represented by the following formula:

(Wherein R ^{4 to} R ⁷ are the same or different and are a hydrogen atom, halogen atom, alkyl group, phenyl group, phenyl group, aralkyl group, fluorinated hydrocarbon group, alkoxy group, aryloxy group, secondary amino group) A group or a tertiary silyl group, and R ^{4 to} R ⁷ may be optionally bonded.)

(Wherein R ^{1 to} R ³ are the same or different and represent an alkyl group, a phenyl group, or a polycyclic aromatic hydrocarbon group, and at least one of R ^{1 to} R ³ is a polycyclic aromatic hydrocarbon) And A ¹ represents a halogen atom or a hydroxyl group.)

(Wherein R ¹ and R ² are the same or different and represent an alkyl group, a phenyl group, or a polycyclic aromatic hydrocarbon group, and at least one of R ¹ or R ² is a polycyclic aromatic hydrocarbon group; And R ⁸ represents a hydrogen atom or an alkyl group.)